Methane is an important greenhouse gas, and also a widespread source of renewable energy. An improved understanding of the mechanisms of methane metabolism by microbes can lay a solid theoretical foundation for the realization of reduced methane emissions and the more rational utilization of this energy source. Direct electron transfer (DET), mediated by Archaea, is an important pathway involved in methane metabolism, and in recent years it has become a research hotspot in the field of environmental microbiology. In?this?study,?the microorganisms involved in DET during the processes of syntrophic methanogenesis, electromethanogenesis, and anaerobic methane oxidation were?briefly?reviewed,?and their respective mechanisms of doing so were described in detail. DET has been demonstrated to be involved in both methanogenesis and anaerobic oxidation of methane. The former can be classified into two categories according to the electron sources used, which are syntrophic methanogenesis and electromethanogenesis, whereas in the latter process methane is oxidized with electrons transferred from Archaea to an extracellular electron receptor. During the process of methanogenesis, methanogenic Archaea can directly accept extracellular electrons via cytochrome proteins, pili of a partner bacterium, or conductive solids. In contrast, methanotrophic Archaea use cytochrome proteins in their outer membrane to donate electrons to extracellular solids or microbes. For the DET mechanism to be applied to solve practical problems, future studies on Archaea-mediated DET should focus on the components of the electron transport chain of methane metabolism and its interactions with bacteria.